EP1366103A4 - Copolyester a groupes terminaux hautement carboxyles (ceg) et un procede de preparation associe - Google Patents

Copolyester a groupes terminaux hautement carboxyles (ceg) et un procede de preparation associe

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Publication number
EP1366103A4
EP1366103A4 EP01946545A EP01946545A EP1366103A4 EP 1366103 A4 EP1366103 A4 EP 1366103A4 EP 01946545 A EP01946545 A EP 01946545A EP 01946545 A EP01946545 A EP 01946545A EP 1366103 A4 EP1366103 A4 EP 1366103A4
Authority
EP
European Patent Office
Prior art keywords
copolyester
per gram
anhydride
composition
succinic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01946545A
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German (de)
English (en)
Other versions
EP1366103B1 (fr
EP1366103A1 (fr
Inventor
Xiaoyan Huang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista Technologies Sarl
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Invista Technologies SARL Switzerland
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Publication date
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Publication of EP1366103A4 publication Critical patent/EP1366103A4/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides

Definitions

  • the present invention concerns a copolyester resin having a high number of carboxyl end groups (CEG) and a method of making such a resin.
  • the copolyester is polyethylene terephthalate and a dicarboxylic acid, along with an anhydride resulting in a high content CEG resin characterized by reduced stress cracking.
  • the copolyester is employed for a packaging resin useful in such as a soft drink beverage bottle, for example, with significantly improved stress cracking resistance.
  • the present invention also concerns a method of producing the copolyester by introducing at the end of polycondensation, one or more of phthalic anhydride, glutaric anhydride, benzoic anhydride, maleic anhydride or succinic anhydride in an amount sufficient to significantly reduce the caustic stress cracking.
  • Copolyester bottle resin is well known in the art.
  • Typical copolyester bottle resins employ polyethylene terephthalate (PET) and a dicarboxylic acid such as isophthalic acid.
  • PET polyethylene terephthalate
  • the dicarboxylic acid was added to adjust the rate of crystallization of PET by decreasing it, in order to obtain clear bottle/jar preforms, which are stretch-blow molded into containers, such as soft drink bottles. If a crystallization retarding agent is not employed, crystallization of the preform occurs resulting in a hazy preform and a hazy bottle/jar.
  • too much dicarboxylic acid is used, the physical properties of copolyester resin are significantly weaker than PET resin.
  • the smaller (e.g. 20 ounce) soft drink beverage bottles which have a larger volume/surface area ratio, require a higher barrier property than (2 liter) bottles.
  • the resin composition for smaller soft drink bottles contains more isophthalic acid to improve the barrier properties, than larger bottles.
  • U.S. Patent 3,051,212 to Daniels; U.S Patent 4,016,142 to Alexander et al.; and U.S. Patent 4,442,058 to Griffith et al. teach reducing the amount of CEG present in polyester in order to increase the hydrolytic stability. More specifically, these references recognize that an increase in the CEG content for polyester, decreases the hydrolytic stability of the polymer, such that the IV stability during drying decreases, i.e., the IV drops during drying.
  • U.S. Patent 4,328,593 to Duh discloses an amorphous polyester which has an optimal level of CEG to reduce the reaction time in a solid state polymerization vessel. Reducing the reaction time in a solid state polymerization (SSP) vessel minimizes chemical instability and deleterious polymerization byproducts.
  • the optimum amount is defined as the amount of CEG content in the amorphous polymer necessary to react with some of the HEG (hydroxyl end groups) to favor the chemical reaction rate.
  • polyester resin (of the preform or the blown bottle) contains a high CEG content. Polyester resin is polymer which has been solid state polymerized.
  • U.S. Patent 4,361,681 to Bernhardt discloses PET having a reduced acetaldehyde generation rate.
  • the PET is reacted with succinic or phthalic anhydride.
  • the examples disclose that the anhydride was introduced by physically precoating the resin (which had been solid state polymerized) just prior to extrusion into bottle preforms. There is no disclosure relating to copolyesters or the CEG content.
  • U.S. Patent 4,578,437 to Light et al. discloses copolyesters useful for bottle resin. Specifically, this reference discloses PET made from terephthalic acid and ethylene glycol with isophthalic acid to create the copolyester. This reference discloses its copolyesters have improved carbon dioxide barrier properties for soft drinks.
  • U.S. Patent 5,362,844 to Kerpes et al. discloses an amorphous PET resin useful for making bottles, which has an optimum CEG content and after the PET has been SSP'd the resulting resin has a low acetaldehyde content. It is known that the CEG content in an amorphous polyester will be significantly reduced during solid state polymerization. There is no disclosure that the polyester resin, preform, or the bottle contains a high CEG content.
  • U.S. Patent 5,912,307 and 6,011,132 to Paschke et al. discloses a copolyester of PET, naphthalate and/or isophthalate to increase the crystallinity of the copolyester article thereby exhibiting high carbon dioxide barrier properties.
  • U.S. Patent 5,925,710 to Wu et al. teaches copolyesters having 2.5 weight percent of isophthalic acid. These copolyesters are useful for bottle resin. This reference discloses the amount of CEG in the amorphous resin, but does not disclose the amount of CEG in the preform or bottle (i.e., after solid state polymerization).
  • PCT published application WO 00/49065 to DuPont discloses a PET - isophthalic acid comonomer having a very high CEG content which was solid state polymerized for up to 24 hours.
  • the IV never exceeded 0.639 because the HEG were essentially depleted, limiting further molecular weight enhancement.
  • This reference also teaches that low CEG content is better for producing high IV's (see Examples 2 and 5).
  • the resin of the present invention directed to a copolyester of PET and at least one dicarboxylic acids such as, for example, isophthalic acid or naphthoic acid has a reduced stress cracking i.e. improved stress cracking performance when small amounts of phthalic, glutaric, benzoic, maleic and/or succinic anhydride are incorporated into the copolyester.
  • the anhydride reacts with the HEG in the copolyester to produce CEG. It is believed that these higher CEG resins neutralize the alkaline lubricants that contact the base of the bottle. Therefore, the incorporation of anhydride into the resin to convert some of the HEG to CEG drastically reduces the stress cracking occurring in soft drink bottles, for example.
  • the stress cracking is exemplified when a bottle bursts, discharging its contents.
  • the present invention refers to a copolyester composition consisting of PET and dicarboxylic acid such as isophthalic acid or naphthoic acid, which has been solid stated, and wherein the copolyester contains up to 20 wt % of the dicarboxylic acid and has a CEG content greater than 25 microequivalents per gram.
  • Solid state resin means a resin having an IV greater than about 0.65. More preferably, the copolyester compositions of the present invention have an IV greater than about 0.70. Most preferably, the copolyester compositions of the present invention have an IV greater than about 0.75.
  • the broad scope of the present invention contemplates a CEG value of 25 microequivalents per gram, a preferred range is 30 microequivalents per gram, and a most preferred range is 40 microequivalents per gram.
  • the present invention also comprises a method of manufacturing a resin composition having improved (reduced) stress cracking by producing a copolymer of PET and dicarboxylic acid such as isophthalic acid or naphthoic acid, and adding at least one of phthalic anhydride, glutaric anhydride, benzoic anhydride, maleic anhydride or succinic anhydride as a late addition in the melt polymerization process, and solid state polymerizing the composition.
  • phthalic anhydride glutaric anhydride
  • benzoic anhydride maleic anhydride or succinic anhydride
  • PET Polyethylene terephthalate
  • ethylene glycol for example, via an esterification reaction, followed by a polycondensation reaction.
  • the reactions can be driven to near completion, yielding PET having up to 3 weight percent of diethylene glycol and other byproducts. Pet is meant to include small amounts of byproducts.
  • PET Conventional continuous production of PET is well known in the art and comprises reacting terephthalic acid and ethylene glycol at a temperature of approximately 200° to 250° C forming monomer and water. Because the reaction is reversible, the water is continuously removed, driving the reaction to the production of monomers. Next the monomers undergo polycondensation reaction in vacuum conditions at a temperature of approximately 250° to 290°C to form polymer having an IV of about 0.4 to 0.6. During the esterification reaction, no catalyst is needed. However, in the polycondensation reaction, a catalyst such as antimony or titanium is necessary.
  • PET is also made in batch and continuous processes from the reaction of the ester-dimethyl terephthalate and ethylene glycol, at a reaction temperature of approximately 190° to 230°C forming alcohol (methanol) and monomer.
  • This esterification reaction is reversible and the alcohol must be continuously removed, driving the reaction to the production of monomer.
  • catalysts such as manganese, zinc, cobalt or other conventional catalyst are employed.
  • the monomer undergoes a polycondensation reaction at the conditions stated above to form a polymer having an IV of about 0.4 to 0.6.
  • Suitable diacids may be aliphatic, alicyclic, or aromatic dicarboxylic acids such as isophthalic acid, 1,4- cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid; 2,6-naphthalenedicarboxylic acid, bibenzoic acid, oxalic acid, malonic acid, pimelic acid, suberic acid, azalaic acid, maleic acid, fumaric acid, phthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, or mixtures of these and their equivalents.
  • aromatic dicarboxylic acids such as isophthalic acid, 1,4- cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adip
  • Bottle resin typically contains 1.5 - 20 wt.%, based on the weight of the resin, of isophthalic acid as the crystalization retarder and barrier improvement additive.
  • Typical additives to increase the CEG level of the copolyester are phthalic, glutaric, benzoic, maleic and/or succinic anhydride.
  • the ester and acid equivalents of these anhydrides are not desirable because a catalyst would be necessary for these to react with the resin. For example, if dimethyl phthalate was employed, it would not react with the copolyester resin at the end of polycondensation without the presence of a catalyst.
  • Using the anhydrides to increase CEG eliminates the need for any catalyst.
  • An additional advantage of the use of anhydrides is that no byproducts are generated by their reaction with HEG. Reaction of esters would generate alcohols and reaction of diacids would generate water.
  • the amount of anhydride typically employed in the present invention ranges from about 10 - 100 microequivalents, and preferably 20 to 50 microequivalents per gram of the copolyester.
  • the first reaction is a slower reaction but water is easily separated from the reaction vessel.
  • the second reaction is faster but the glycol is harder to separate from the reactor. From these two equations, it is easy to see that if the anhydride reacts with all of the hydroxyls in the copolyester, there will be no more OH groups (hydroxyl end groups) available for polymerization. Accordingly, the reaction will stop.
  • anhydride is introduced late in the melt polymerization process such as late in the polycondensation process just prior to solid state polymerization.
  • the anhydride could be added near the end of the polycondensation polymerization process such that it has at least one to two minutes reaction time before the copolymer is extruded, cooled and cut into chip. If a batch process is used, there are two reactor vessels, one for esterification, which is generally at atmospheric pressure and at a temperature of from about 180° to 250 ° C.
  • esterified reaction products are transferred to a polycondensation vessel, which is operated at a higher temperature, generally between 250° to 290°C and at a vacuum.
  • a polycondensation vessel which is operated at a higher temperature, generally between 250° to 290°C and at a vacuum.
  • the anhydride of the present invention would be added to copolyester resin at the end of polycondensation reaction, just -after the vacuum is permitted to attain atmospheric pressure, such that it reacts with the copolymer for at least one to two minutes before it is extruded, cooled and cut into chip.
  • anhydride is added to the transfer pipe between the final polymerizer and the die that forms the strands that are cooled and cut into chips.
  • Anhydride added at this point has a mixing time of about one to two minutes (the residence time) in the piping as it flows from the high polymerizer vessel to the die where it is extruded, then cooled and cut into chip.
  • the amount of anhydride incorporated at this point in the process can be controlled to give an optimum CEG/HEG ratio sufficient for solid state polymerization, i.e., some residual HEG, as well as an increased CEG level in the final polyester resin.
  • 10 - 100 microequivalents of the anhydride is employed per gram of the resin.
  • 20 - 50 microequivalents of anhydride is used per gram of the copolyester resin.
  • the copolyester is extruded, cooled and cut into chip as conventionally known in the art.
  • the chip is ready for SSP, where the chip IV is generally increased from about 0.4-0.6 to 0.65-0.90. For a 0.6 IN., a total of about 110 end groups are present. There are about 80 HEG (microequivalents per gram) and about 30 CEG (microequivalents per gram) present from a typical melt phase polymerization.
  • the CEG value of a polymer is determined by dissolving a sample of the polymer in reagent grade benzyl alcohol and titrating to the purple end point of phenol red indicator with 0.03 N sodium hydroxide/benzyl alcohol solution. The results are reported in microequivalents sodium hydroxide per gram of the sample.
  • the DEG (diethylene glycol) content of the polymer is determined by hydrolyzing the polymer with an aqueous solution of ammonium hydroxide in a sealed reaction vessel at 220+5 °C for approximately two hours. The liquid portion of the hydrolyzed product is then analyzed by gas chromatography.
  • the gas chromatography apparatus is a FID Detector (HP5890, HP7673A) from Hewlett Packard.
  • the ammonium hydroxide is 28 to 30 % by weight ammonium hydroxide from Fisher Scientific and is reagent grade.
  • the resistance of a bottle to stress cracking is determined at an accelerated test using sodium hydroxide to induce stress cracking. Twenty-five bottles are used as a set. The bottles are filled with water at 22° C to a target net contents (2 liter bottles would contain 2 liters of water). Each bottle is pressurized with compressed air to an equivalent internal pressure of 531 kPa (77 psi). Five minutes after pressurization, each bottle is placed in individual pockets containing a 0.2 percent sodium hydroxide solution at 22°C. The solution covers the base of the bottle up to the top of the strap of the bottle. The time for failure of each bottle is recorded. Failure is defined as a burst or slow leak as evidenced by a drop in the level of water in the bottle. The test is completed after four hours. Results are reported as the number of failures in a four hour period, and as the average time for thus said to fail.
  • the haze of the preforms was measured with a Hunter Lab ColorQuest II instrument.
  • the haze is defined as the percent of diffused light to total transmitted light.
  • the resin of the present invention is typically heated and extruded into preforms.
  • Each preform for a 20 ounce soft drink bottle employs about 26.8 grams of the resin.
  • the preform is then heated to about 100 - 120 ° C and blown-molded into a 20 ounce contour bottle at a stretch ratio of about 12.5.
  • the stretch ratio is the stretch in the radial direction times the stretch in the length (axial) direction.
  • a preform may be stretched about two times its length and stretched about six times is diameter giving a stretch ratio of twelve (2 x 6). Since the bottle size is fixed, different preform sizes can be used for obtaining different stretch ratios.
  • the preforms tested in the examples for the 20 ounce contour bottles have from 5.0 to 5.4 grams of resin in the base. More specifically, the weight of the bottle base was primarily from 5.2 to 5.3 grams. Most stress cracking occurs in the base of the bottle. Testing for stress cracking should be completed with bottles having a base of about the same thickness (i.e., the same amount of resin) to give comparable results.
  • EXAMPLE 1 A copolyester of PET and 2% by weight (based on weight of copolyester) isophthalic acid was formed using terephthalic acid, isophthalic acid and ethylene glycol in a continuous process with about 200 ppm antimony catalyst and about 10 ppm phosphorus (added as polyphosphoric acid). The diethylene glycol (DEG) level of the copolyester was about 1.5 weight percent. Succinic anhydride was melt metered into the molten copolymer after the last polymerizer before extrusion and pelletization giving a residence time of about one minute. The amounts of succinic anhydride are set forth in Table 1.
  • EXAMPLE 2 A copolyester of PET containing 3 weight percent based on the weight of copolyester of isophthalate was prepared in a batch DMT process. Isophthalic acid was added after ester exchange using 80 ppm Mn manganese catalyst and 50 ppm phosphorus as a sequestering agent. The monomer was polymerized using about 200 ppm antimony catalyst. Various amounts of succinic anhydride were added at the end of polymerization by releasing the vacuum, adding and mixing under a nitrogen atmosphere for four minutes prior to extrusion and pelletization. The DEG level of the copolyesters were about one weight percent. The results are set forth below.
  • EXAMPLE 3 A copolyester of PET was prepared containing 8.6 weight percent isophthalate based on weight of coplyester was prepared as in Example 2. The DEG content of the copolyesters was about 0.8 weight %. The data for these tests is set forth in Table 3.
  • EXAMPLE 4 A series of copolymers were prepared according to Example 2, but using different anhydrides. The DEG level of the copolyesters was about 1.2 to 1.5 weight %. The results are shown in Table 4. Table 4
  • This Example shows the use of different anhydrides for increasing the CEG content of the copolyester resin.
  • COMPARATIVE EXAMPLE 5 A series of copolymers containing either phthalic or isophthalic acid were prepared by a batch DMT process. Either dimethyl phthalate or dimethyl isophthalate was reacted with ethylene glycol and esterified with manganese acetate (82 ppm Mn) and antimony trioxide (314 ppm Sb) at a temperature range of about 180-220°C with methanol removal. After the addition of polyphosphoric acid (82 ppm P) the esterified product was polymerized in a vacuum (ultimately 0.3 Torr) at a temperature of 285°C to an IV of 0.60 to 0.64.
  • a vacuum ultimately 0.3 Torr
  • amorphous copolyesters were dried and compression molded at 265°C for 5 min. at 20,000 psi to remove air bubbles while forming thin films.
  • the oxygen permeability (cc cm/m 2 /atm day) of these films were calculated from measurements of the steady state flux with a MOCON OX-TRANO 2/20 instrument using Fick's law. The oxygen flux was measured at 25°, 0% relative humidity, and at 1 atmospheric pressure. The samples were conditioned with nitrogen for 24 hours to remove all oxygen before measuring the flux.
  • the oxygen permeability of these polyesters are given in Table 5, showing that phthalate esters are more effective, at the same mole %, in barrier properties than isophthalate copolyesters.
  • phthalic anhydride also decreases the rate of crystallization of PET, such that one skilled in the art would not be led to modify a PET and anhydride copolymer by the addition of isophthalic acid for crystallization improvements.
  • Bottle haze employing the method of the present invention is a significant improvement (see Example 1) over the process disclosed by the Bernhardt reference as seen from Table 6.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition comprenant: un copolyester de polyéthylène téréphtalate et un acide dicarboxylique ou son équivalent ester, et pas plus de 100 microéquivalents par gramme du copolyester d'un anhydride sélectionné dans la classe renfermant des anhydrides succinique, glutarique, benzoïque, maléïque et phtalique, cette composition possédant une teneur en CEG supérieure à environ 25 microéquivalents par gramme et une viscosité intrinsèque supérieure à environ 0.65. L'invention concerne également un procédé de préparation d'une composition présentant une fissure de contrainte, due à l'alcalinité, réduite. Ce procédé consiste: à faire réagir de l'acide téréphtalique ou son équivalent ester et un autre acide dicarboxylique avec de l'éthylène glycol par estérification suivie d'une polycondensation, de manière à obtenir un copolyester de polyéthylène téréphtalate; à ajouter à la fin de la polycondensation pas plus de 100 microéquivalents par gramme en fonction du copolyester d'un anhydride sélectionné dans la classe renfermant des anhydrides succinique, glutarique, benzoïque, maléïque et phtalique, cette composition possédant une teneur en CEG supérieure à environ 25 microéquivalents par gramme.
EP01946545A 2000-12-06 2001-06-20 Copolyester a haute teneur en groupes terminaux carboxyles (ceg) et procede de preparation associe Expired - Lifetime EP1366103B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US731414 2000-12-06
US09/731,414 US6342578B1 (en) 2000-12-06 2000-12-06 Copolyester with high carboxyl end groups and a method for making
PCT/US2001/019610 WO2002046265A1 (fr) 2000-12-06 2001-06-20 Copolyester a groupes terminaux hautement carboxyles (ceg) et un procede de preparation associe

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EP1366103A1 EP1366103A1 (fr) 2003-12-03
EP1366103A4 true EP1366103A4 (fr) 2006-04-26
EP1366103B1 EP1366103B1 (fr) 2009-08-05

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US (1) US6342578B1 (fr)
EP (1) EP1366103B1 (fr)
KR (1) KR100564258B1 (fr)
CN (1) CN1218982C (fr)
AU (1) AU2001268576A1 (fr)
BR (1) BR0113963B1 (fr)
CA (1) CA2419621C (fr)
DE (1) DE60139509D1 (fr)
ES (1) ES2329548T3 (fr)
MX (1) MXPA03002782A (fr)
RU (1) RU2262517C2 (fr)
WO (1) WO2002046265A1 (fr)

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EP1054031A2 (fr) * 1999-05-21 2000-11-22 Ciba SC Holding AG Augmentation de la masse moléculaire et modification de polymères de condensation

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JPS5328649A (en) * 1976-08-31 1978-03-17 Teijin Ltd Polyester composition
US4238593A (en) * 1979-06-12 1980-12-09 The Goodyear Tire & Rubber Company Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optimal carboxyl content
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US4361681A (en) * 1980-11-03 1982-11-30 The Goodyear Tire & Rubber Company Polyethylene terephthalate having a reduced acetaldehyde generation rate
EP0819716A2 (fr) * 1996-07-18 1998-01-21 SINCO ENGINEERING S.p.A. Procédé amélioré pour la production de polyesters
JPH10212345A (ja) * 1997-01-29 1998-08-11 Teijin Ltd 成形性に優れたポリエステルの製造方法
EP1054031A2 (fr) * 1999-05-21 2000-11-22 Ciba SC Holding AG Augmentation de la masse moléculaire et modification de polymères de condensation

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BR0113963B1 (pt) 2011-02-22
KR20030094212A (ko) 2003-12-11
MXPA03002782A (es) 2003-07-28
RU2262517C2 (ru) 2005-10-20
KR100564258B1 (ko) 2006-03-29
CA2419621C (fr) 2007-01-09
US6342578B1 (en) 2002-01-29
CN1218982C (zh) 2005-09-14
EP1366103B1 (fr) 2009-08-05
CA2419621A1 (fr) 2002-06-13
WO2002046265A1 (fr) 2002-06-13
CN1483054A (zh) 2004-03-17
AU2001268576A1 (en) 2002-06-18
DE60139509D1 (de) 2009-09-17
ES2329548T3 (es) 2009-11-27
BR0113963A (pt) 2003-07-29
EP1366103A1 (fr) 2003-12-03

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